U.S. patent application number 14/448645 was filed with the patent office on 2015-02-19 for photosensitive polysiloxane composition and uses thereof.
The applicant listed for this patent is CHI MEI CORPORATION. Invention is credited to CHUN-AN SHIH, MING-JU WU.
Application Number | 20150050596 14/448645 |
Document ID | / |
Family ID | 52467082 |
Filed Date | 2015-02-19 |
United States Patent
Application |
20150050596 |
Kind Code |
A1 |
WU; MING-JU ; et
al. |
February 19, 2015 |
PHOTOSENSITIVE POLYSILOXANE COMPOSITION AND USES THEREOF
Abstract
The invention relates to a photosensitive polysiloxane
composition and a thin film formed by the aforementioned
photosensitive polysiloxane composition. The thin film is a
planarization film of a TFT substrate, an interlayer insulating
film or an overcoat of a core material or a protective material in
a waveguide. The photosensitive polysiloxane composition has
excellent chemical resistance. The photosensitive polysiloxane
composition comprises a polysiloxane (A), an o-naphthoquinone
diazide sulfonic acid ester (B), a thermal base generator (C) and a
solvent (D).
Inventors: |
WU; MING-JU; (TAINAN CITY,
TW) ; SHIH; CHUN-AN; (TAINAN CITY, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CHI MEI CORPORATION |
TAINAN CITY |
|
TW |
|
|
Family ID: |
52467082 |
Appl. No.: |
14/448645 |
Filed: |
July 31, 2014 |
Current U.S.
Class: |
430/287.1 |
Current CPC
Class: |
G03F 7/30 20130101; G03F
7/0007 20130101; G03F 7/038 20130101; G03F 7/022 20130101; G03F
7/0226 20130101; G03F 7/09 20130101; G03F 7/0757 20130101; G03F
7/0233 20130101; G03F 7/0005 20130101 |
Class at
Publication: |
430/287.1 |
International
Class: |
G03F 7/075 20060101
G03F007/075; G03F 7/16 20060101 G03F007/16 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 13, 2013 |
TW |
102128929 |
Claims
1. A photosensitive polysiloxane composition comprising: a
polysiloxane (A); an o-naphthoquinone diazide sulfonic acid ester
(B); a thermal base generator (C); and a solvent (D); wherein: the
thermal base generator (C) comprises a compound represented by
Formula (1) or an salt derivative thereof and/or a compound
represented by Formula (2) and/or a compound represented by Formula
(3): ##STR00013## wherein: m represents an integer selected from 2
to 6; R.sup.1 and R.sup.2 independently represent a hydrogen atom,
a C.sub.1-C.sub.8 alkyl group, a substituted or unsubstituted
C.sub.1-C.sub.6 hydroxyalkyl group, or a C.sub.2-C.sub.12
dialkylamino group; ##STR00014## wherein: R.sup.3, R.sup.4, R.sup.5
and R.sup.6 independently represent a hydrogen atom, a substituted
or unsubstituted C.sub.1-C.sub.8 alkyl group, a substituted or
unsubstituted C.sub.3-C.sub.8 cycloalkyl group, a substituted or
unsubstituted C.sub.1-C.sub.8 alkoxy group, a substituted or
unsubstituted C.sub.2-C.sub.8 alkenyl group, a substituted or
unsubstituted C.sub.2-C.sub.8 alkynyl group, a substituted or
unsubstituted aryl group, or a substituted or unsubstituted
heterocyclic group; R.sup.7 and R.sup.8 independently represent a
hydrogen atom, a substituted or unsubstituted C.sub.1-C.sub.8 alkyl
group, a substituted or unsubstituted C.sub.3-C.sub.8 cylcoalkyl
group, a substituted or unsubstituted C.sub.1-C.sub.8 alkoxy group,
a substituted or unsubstituted C.sub.2-C.sub.8 alkenyl group, a
substituted or unsubstituted C.sub.2-C.sub.8 alkynyl group, a
substituted or unsubstituted aryl group, or a substituted or
unsubstituted heterocyclic group, or R.sup.7 and R.sup.8 together
form a substituted or unsubstituted monocyclic group, or R.sup.7
and R.sup.8 together form a substituted or unsubstituted polycyclic
group; R.sup.9 represents a substituted or unsubstituted
C.sub.1-C.sub.12 alkyl group, a substituted or unsubstituted
C.sub.3-C.sub.12 cycloalkyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkynyl group, an unsubstituted aryl group, an
aryl group substituted with a C.sub.1-C.sub.3 alkyl group, an
unsubstituted aralkyl, an aralkyl group substituted with a
C.sub.1-C.sub.3 alkyl group or a substituted or unsubstituted
heterocyclic group; the total carbon atom amount of R.sup.9 is
below 12; ##STR00015## wherein: R.sup.3, R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 are as defined in Formula (2); R.sup.10
represents a substituted or unsubstituted C.sub.1-C.sub.12 alkylene
group, a substituted or unsubstituted C.sub.3-C.sub.12
cycloalkylene group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkenylene group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkynylene group, an unsbustituted arylene group,
an arylene group substituted with a C.sub.1-C.sub.3 alkyl group, an
unsubstituted aralkylene group, an aralkylene group substituted
with a C.sub.1-C.sub.3 alkyl group or a substituted or
unsubstituted heterocyclic group; the total carbon atom amount of
R.sup.10 is below 12.
2. The photosensitive polysiloxane composition according to claim
1, wherein the polysiloxane (A) is a copolymer obtained by
hydrolyzing and partial condensing a silane monomer component
represented by Formula (4); Si(R.sub.a).sub.W(OR.sub.b).sub.4-w
Formula (4), wherein: at least one of R.sub.a represents an alkyl
group substituted with an acid anhydride group, an alkyl group
substituted with an epoxy group and/or an alkoxy group substituted
with an epoxy group; other R.sub.a represents a hydrogen atom, a
C.sub.1-C.sub.10 alkyl group, a C.sub.2-C.sub.10 alkenyl group, a
C.sub.6-C.sub.15 aryl group; each R.sub.a is the same or different;
R.sub.b represents a hydrogen atom, a C.sub.1-C.sub.6 alkyl group,
a C.sub.1-C.sub.6 acyl group, a C.sub.6-C.sub.15 aryl group; each
R.sub.b is the same or different; and w represents an integer from
0 to 3.
3. The photosensitive polysiloxane composition according to claim
1, wherein based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the o-naphthoquinone diazide
sulfonic acid ester (B) is from 1 part by weight to 30 parts by
weight.
4. The photosensitive polysiloxane composition according to claim
1, wherein based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the thermal base generator (C)
is from 0.05 parts by weight to 20 parts by weight.
5. The photosensitive polysiloxane composition according to claim
1, wherein based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the solvent (D) is from 100
parts by weight to 1200 parts by weight.
6. A method for forming a thin film on a substrate comprising
applying the photosensitive polysiloxane composition according to
claim 1 on the substrate.
7. The method according to claim 6, wherein the polysiloxane (A) is
a copolymer obtained by hydrolyzing and partial condensing a silane
monomer component represented by Formula (4);
Si(R.sub.a).sub.W(OR.sub.b).sub.4-w Formula (4), wherein: at least
one of R.sub.a represents an alkyl group substituted with an acid
anhydride group, an alkyl group substituted with an epoxy group
and/or an alkoxy group substituted with an epoxy group; other
R.sub.a represents a hydrogen atom, a C.sub.1-C.sub.10 alkyl group,
a C.sub.2-C.sub.10 alkenyl group, a C.sub.6-C.sub.15 aryl group;
each R.sub.a is the same or different; R.sub.b represents a
hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6
acyl group, a C.sub.6-C.sub.15 aryl group; each R.sub.b is the same
or different; and w represents an integer from 0 to 3.
8. The method according to claim 6, wherein based on 100 parts by
weight of the used amount of the polysiloxane (A), the used amount
of the o-naphthoquinone diazide sulfonic acid ester (B) is from 1
part by weight to 30 parts by weight.
9. The method according to claim 6, wherein based on 100 parts by
weight of the used amount of the polysiloxane (A), the used amount
of the thermal base generator (C) is from 0.05 parts by weight to
20 parts by weight.
10. The method according to claim 6, wherein based on 100 parts by
weight of the used amount of the polysiloxane (A), the used amount
of the solvent (D) is from 100 parts by weight to 1200 parts by
weight.
11. A thin film on a substrate, which is manufactured by the method
according to claim 6.
12. The thin film according to claim 11, wherein the polysiloxane
(A) is a copolymer obtained by hydrolyzing and partial condensing a
silane monomer component represented by Formula (4);
Si(R.sub.a).sub.W(OR.sub.b).sub.4-w Formula (4), wherein: at least
one of R.sub.a represents an alkyl group substituted with an acid
anhydride group, an alkyl group substituted with an epoxy group
and/or an alkoxy group substituted with an epoxy group; other
R.sub.a represents a hydrogen atom, a C.sub.1-C.sub.10 alkyl group,
a C.sub.2-C.sub.10 alkenyl group, a C.sub.6-C.sub.15 aryl group;
each R.sub.a is the same or different; R.sub.b represents a
hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6
acyl group, a C.sub.6-C.sub.15 aryl group; each R.sub.b is the same
or different; and w represents an integer from 0 to 3.
13. The thin film according to claim 11, wherein based on 100 parts
by weight of the used amount of the polysiloxane (A), the used
amount of the o-naphthoquinone diazide sulfonic acid ester (B) is
from 1 part by weight to 30 parts by weight.
14. The thin film according to claim 11, wherein based on 100 parts
by weight of the used amount of the polysiloxane (A), the used
amount of the thermal base generator (C) is from 0.05 parts by
weight to 20 parts by weight.
15. The thin film according to claim 11, wherein based on 100 parts
by weight of the used amount of the polysiloxane (A), the used
amount of the solvent (D) is from 100 parts by weight to 1200 parts
by weight.
16. The thin film according to claim 11, wherein the thin film is a
planarization film of a TFT substrate in a liquid crystal display
element or organic light-emitting display device, an interlayer
insulating film or an overcoat of a core material or a protective
material in a waveguide.
17. A device comprising the thin film according to claim 11.
18. The device according to claim 17, wherein the thin film is a
planarization film of a TFT substrate in a liquid crystal display
element or organic light-emitting display device, an interlayer
insulating film or an overcoat of a core material or a protective
material in a waveguide.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention relates to a photosensitive polysiloxane
composition and a thin film and device formed by the aforementioned
photosensitive polysiloxane composition. The thin film is a
planarization film of a TFT substrate in a liquid crystal display
element or organic light-emitting display device, an interlayer
insulating film or an overcoat of a core material or a protective
material in a waveguide. More particularly, the invention is to
provide a photosensitive polysiloxane composition having excellent
chemical resistance after exposing and developing.
[0003] 2. Description of the Related Art
[0004] In recent years, in the field of the semiconductor industry,
liquid crystal displays (LCDs) and organic electro-luminescence
displays (OELDs), with the size reduction, the demand of the
miniaturization of the pattern(s) in the photolithography process
is increased. Generally, the miniaturized pattern is formed by
exposing and developing a positive photosensitive composition
having high resolution and high photosensitivity; wherein, a
positive photosensitive composition using a polysiloxane as the
main component has become the mainstream in this field.
[0005] Japanese Patent Publication No. 2008-107529 discloses a
photosensitive composition for a curing film of a high degree of
transparency. The photosensitive composition uses a polysiloxane
comprising oxetanyl or oxydicarbonyl groups, which form a
hydrophilic structure through a ring-opening reaction in a
copolymerization. Although the photosensitive composition has high
solubility in a weak alkaline developer, the poor chemical
resistance of the photosensitive composition can not be accepted in
this field.
[0006] Therefore, a photosensitive polysiloxane composition that
enhances the chemical resistance at the same time is a target
remained to be achieved.
SUMMARY OF THE INVENTION
[0007] In the present invention, a specific polysiloxane and
thermal base generator are provided to obtain a photosensitive
polysiloxane composition having good chemical resistance.
[0008] Therefore, the invention relates to a photosensitive
polysiloxane composition comprising:
[0009] a polysiloxane (A);
[0010] an o-naphthoquinone diazide sulfonic acid ester (B);
[0011] a thermal base generator (C); and
[0012] a solvent (D);
[0013] wherein:
[0014] the thermal base generator (C) comprises a compound
represented by Formula (1) or an salt derivative thereof and/or a
compound represented by Formula (2) and/or a compound represented
by Formula (3):
##STR00001##
[0015] wherein:
[0016] m represents an integer selected from 2 to 6;
[0017] R.sup.1 and R.sup.2 independently represent a hydrogen atom,
a C.sub.1-C.sub.8 alkyl group, a substituted or unsubstituted
C.sub.1-C.sub.6 hydroxyalkyl group, or a C.sub.2-C.sub.12
dialkylamino group;
##STR00002##
[0018] wherein:
[0019] R.sup.3, R.sup.4, R.sup.5 and R.sup.6 independently
represent a hydrogen atom, a substituted or unsubstituted
C.sub.1-C.sub.8 alkyl group, a substituted or unsubstituted
C.sub.3-C.sub.8 cycloalkyl group, a substituted or unsubstituted
C.sub.1-C.sub.8 alkoxy group, a substituted or unsubstituted
C.sub.2-C.sub.8 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.8 alkynyl group, a substituted or unsubstituted aryl
group, or a substituted or unsubstituted heterocyclic group;
[0020] R.sup.7 and R.sup.8 independently represent a hydrogen atom,
a substituted or unsubstituted C.sub.1-C.sub.8 alkyl group, a
substituted or unsubstituted C.sub.3-C.sub.8 cylcoalkyl group, a
substituted or unsubstituted C.sub.1-C.sub.8 alkoxy group, a
substituted or unsubstituted C.sub.2-C.sub.8 alkenyl group, a
substituted or unsubstituted C.sub.2-C.sub.8 alkynyl group, a
substituted or unsubstituted aryl group, or a substituted or
unsubstituted heterocyclic group, or R.sup.7 and R.sup.8 together
form a substituted or unsubstituted monocyclic group, or R.sup.7
and R.sup.8 together form a substituted or unsubstituted polycyclic
group; the total carbon atom amount of R.sup.7 and R.sup.8 are
below 10;
[0021] R.sup.9 represents a substituted or unsubstituted
C.sub.1-C.sub.12 alkyl group, a substituted or unsubstituted
C.sub.3-C.sub.12 cycloalkyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkynyl group, an unsubstituted aryl group, an
aryl group substituted with a C.sub.1-C.sub.3 alkyl group, an
unsubstituted aralkyl, an aralkyl group substituted with a
C.sub.1-C.sub.3 alkyl group or a substituted or unsubstituted
heterocyclic group; the total carbon atom amount of R.sup.9 is
below 12.
##STR00003##
[0022] wherein:
[0023] R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are
as defined in Formula (2);
[0024] R.sup.10 represents a substituted or unsubstituted
C.sub.1-C.sub.12 alkylene group, a substituted or unsubstituted
C.sub.3-C.sub.12 cycloalkylene group, a substituted or
unsubstituted C.sub.2-C.sub.12 alkenylene group, a substituted or
unsubstituted C.sub.2-C.sub.12 alkynylene group, an unsbustituted
arylene group, an arylene group substituted with a C.sub.1-C.sub.3
alkyl group, an unsubstituted aralkylene group, an aralkylene group
substituted with a C.sub.1-C.sub.3 alkyl group or a substituted or
unsubstituted heterocyclic group; the total carbon atom amount of
R.sup.10 is below 12.
[0025] The present invention also provides a method for forming a
thin film on a substrate comprising applying the photosensitive
polysiloxane composition as mentioned above on the substrate.
[0026] The present invention also provides a thin film on a
substrate, which is manufactured by the method as mentioned
above.
[0027] The present invention further provides an device comprising
the thin film as mentioned above.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The invention relates to a photosensitive polysiloxane
composition comprising:
[0029] a polysiloxane (A);
[0030] an o-naphthoquinone diazide sulfonic acid ester (B);
[0031] a thermal base generator (C); and
[0032] a solvent (D);
[0033] wherein:
[0034] the thermal base generator (C) comprises a compound
represented by Formula (1) or an salt derivative thereof and/or a
compound represented by Formula (2) and/or a compound represented
by Formula (3):
##STR00004##
[0035] wherein:
[0036] m represents an integer selected from 2 to 6;
[0037] R.sup.1 and R.sup.2 independently represent a hydrogen atom,
a C.sub.1-C.sub.8 alkyl group, a substituted or unsubstituted
C.sub.1-C.sub.6 hydroxyalkyl group, or a C.sub.2-C.sub.12
dialkylamino group;
##STR00005##
[0038] wherein:
[0039] R.sup.3, R.sup.4, R.sup.5 and R.sup.6 independently
represent a hydrogen atom, a substituted or unsubstituted
C.sub.1-C.sub.8 alkyl group, a substituted or unsubstituted
C.sub.3-C.sub.8 cycloalkyl group, a substituted or unsubstituted
C.sub.1-C.sub.8 alkoxy group, a substituted or unsubstituted
C.sub.2-C.sub.8 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.8 alkynyl group, a substituted or unsubstituted aryl
group, or a substituted or unsubstituted heterocyclic group;
[0040] R.sup.7 and R.sup.8 independently represent a hydrogen atom,
a substituted or unsubstituted C.sub.1-C.sub.8 alkyl group, a
substituted or unsubstituted C.sub.3-C.sub.8 cylcoalkyl group, a
substituted or unsubstituted C.sub.1-C.sub.8 alkoxy group, a
substituted or unsubstituted C.sub.2-C.sub.8 alkenyl group, a
substituted or unsubstituted C.sub.2-C.sub.8 alkynyl group, a
substituted or unsubstituted aryl group, or a substituted or
unsubstituted heterocyclic group, or R.sup.7 and R.sup.8 together
form a substituted or unsubstituted monocyclic group, or R.sup.7
and R.sup.8 together form a substituted or unsubstituted polycyclic
group; the total carbon atom amount of R.sup.7 and R.sup.8 are
below 10;
[0041] R.sup.9 represents a substituted or unsubstituted
C.sub.1-C.sub.12 alkyl group, a substituted or unsubstituted
C.sub.3-C.sub.12 cycloalkyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkynyl group, an unsubstituted aryl group, an
aryl group substituted with a C.sub.1-C.sub.3 alkyl group, an
unsubstituted aralkyl, an aralkyl group substituted with a
C.sub.1-C.sub.3 alkyl group or a substituted or unsubstituted
heterocyclic group; the total carbon atom amount of R.sup.9 is
below 12.
##STR00006##
[0042] wherein:
[0043] R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are
as defined in Formula (2);
[0044] R.sup.10 represents a substituted or unsubstituted
C.sub.1-C.sub.12 alkylene group, a substituted or unsubstituted
C.sub.3-C.sub.12 cycloalkylene group, a substituted or
unsubstituted C.sub.2-C.sub.12 alkenylene group, a substituted or
unsubstituted C.sub.2-C.sub.12 alkynylene group, an unsbustituted
arylene group, an arylene group substituted with a C.sub.1-C.sub.3
alkyl group, an unsubstituted aralkylene group, an aralkylene group
substituted with a C.sub.1-C.sub.3 alkyl group or a substituted or
unsubstituted heterocyclic group; the total carbon atom amount of
R.sup.10 is below 12.
[0045] The kind of the polysiloxane (A) is not particularly
limited, as long as the purpose of the present invention can be
fulfilled. Preferably, the polysiloxane (A) is a copolymer obtained
by hydrolyzing and partial condensing a silane monomer component
represented by Formula (4);
Si(R.sub.a).sub.W(OR.sub.b).sub.4-w Formula (4),
[0046] wherein:
[0047] at least one of R.sub.a represents an alkyl group
substituted with an acid anhydride group, an alkyl group
substituted with an epoxy group or an alkoxy group substituted with
an epoxy group; other R.sub.a represents a hydrogen atom, a
C.sub.1-C.sub.10 alkyl group, a C.sub.2-C.sub.10 alkenyl group, a
C.sub.6-C.sub.15 aryl group; each R.sub.a is the same or
different;
[0048] R.sub.b represents a hydrogen atom, a C.sub.1-C.sub.6 alkyl
group, a C.sub.1-C.sub.6 acyl group, a C.sub.6-C.sub.15 aryl group;
each R.sub.b is the same or different; and
[0049] w represents an integer from 0 to 3.
[0050] The C.sub.1-C.sub.10 alkyl group substituted with the acid
anhydride group, for example, is ethyl succinic anhydride, propyl
succinic anhydride or propyl glutaric anhydride
[0051] The C.sub.1-C.sub.10 alkyl group substituted with the epoxy
group, for example, is oxetanylpentyl or
2-(3,4-epoxycyclohexyl)ethyl).
[0052] The alkoxy group substituted with the epoxy group, for
example, is glycidoxypropy or 2-oxetanylbutoxy.
[0053] In the definition of R.sub.b, the C.sub.1-C.sub.6 alkyl
group includes but is not limited to methyl, ethyl, n-propyl,
isopropyl or n-butyl. The C.sub.1-C.sub.6 acyl group includes but
is not limited to acetyl. The C.sub.6-C.sub.15 aryl group includes
but is not limited to phenyl.
[0054] A silane monomer represented by Formula (4) can be used
singly or in combination, and the silane monomer represented by
Formula (4) includes but is not limited to
3-glycidoxypropyltrimethoxysilane (abbreviated as TMS-GAA),
3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl
trimethoxy silane, 2-oxetanylbutoxypropyltriphenoxysilane), the
commercially available products from Toagosei Co., Ltd.:
2-oxetanylbutoxypropyltrimethoxysilane (trade name: TMSOX-D),
2-oxetanylbutoxypropyltriethoxysilane (trade name: TESOX-D),
3-triphenoxysilyl propyl succinic anhydride, the commercially
available products from Shin-Etsu Chemical Co., Ltd.:
3-trimethoxysilyl propyl succinic anhydride (trade name: X-12-967),
the commercially available products from WACKER Co., Ltd:
3-(triethoxysilyl)propyl succinic anhydride (trade name: GF-20),
3-(trimethoxysilyl)propyl glutaric anhydride (abbreviated as TMSG),
3-(triethoxysilyl)propyl glutaric anhydride,
3-(triphenoxysilyl)propyl glutaric anhydride,
diisopropoxy-di(2-oxetanylbutoxy propyl)silane (abbreviated as
DIDOS), di(3-oxetanylpentyl)dimethoxy silane,
(di-n-butoxysilyl)di(propyl succinic anhydride),
(dimethoxysilyl)di(ethyl succinic anhydride),
3-glycidoxypropyldimethylmethoxysilane,
3-glycidoxypropyldimethylethoxysilane,
di(2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxy silane,
tri(2-oxetanylpentyl)methoxy silane, (phenoxysilyl)tri(propyl
succinic anhydride) or (methoxysilyl)di(ethyl succinic
anhydride).
[0055] Preferably, the silane monomer component also comprises a
silane monomer represented by Formula (4-1).
Si(R.sub.c).sub.u(OR.sub.d).sub.4-u Formula (4-1)
[0056] In Formula (4-1), u represents an integer from 0 to 3;
R.sub.c represents hydrogen, a C.sub.1-C.sub.10 alkyl group, a
C.sub.2-C.sub.10 alkenyl group, or a C.sub.6-C.sub.15 aryl group,
and each R.sub.c is the same or different; R.sub.d represents
hydrogen, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 acyl
group, or a C.sub.6-C.sub.15 aryl group, and each R.sub.d is the
same or different.
[0057] In the definition of R.sub.c, the C.sub.1-C.sub.10 alkyl
group, for example, is methyl, ethyl, n-propyl, isopropyl, n-butyl,
tertiary butyl, n-hexyl, n-decyl, trifluoromethyl,
3,3,3-trifluoro-propyl, 3-aminopropyl, 3-mercaptopropyl or
3-isocyanatepropyl. The C.sub.2-C.sub.10 alkenyl group, for
example, is vinyl, 3-acryloxypropyl or 3-methacryloxypropyl. The
C.sub.6-C.sub.15 aryl group, for example, is phenyl, tolyl,
o-hydroxyphenyl, 1-(o-hydroxyphenyl)ethyl,
2-(o-hydroxyphenyl)ethyl,
4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyl or naphthyl.
[0058] In the definition of R.sub.d, the C.sub.1-C.sub.6 alkyl
group, for example, is methyl, ethyl, n-propyl, isopropyl, or
n-butyl. The C.sub.1-C.sub.6 acyl group, for example, is acetyl.
The C.sub.6-C.sub.15 aryl group, for example, is phenyl.
[0059] A silane monomer represented by Formula (4-1) can be used
singly or in combination, and the silane monomer represented by
Formula (4-1) includes but is not limited to tetramethoxysilane,
tetraethoxysilane, tetraacetoxysilane, tetraphenoxy silane,
methyltrimethoxysilane (abbreviated as MTMS),
methyltriethoxysilane, methyltriisopropoxysilane,
methyl-tri-n-butoxysilane, ethyltrimethoxysilane,
ethyltriethoxysilane, ethyltriisopropoxysilane,
ethyltri-n-butoxysilane, n-propyltrimethoxysilane,
n-propyltriethoxysilane, n-butyltrimethoxysilane,
n-butyltriethoxysilane, n-hexyltrimethoxysilane,
n-hexyltriethoxysilane, decyltrimethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane
(abbreviated as PTMS), phenyltriethoxysilane (abbreviated as PTES),
p-hydroxyphenyltrimethoxysilane,
1-(p-hydroxyphenyl)ethyltrimethoxysilane,
2-(p-hydroxyphenyl)ethyltrimethoxysilane,
4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane,
trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
dimethyldimethoxysilane (abbreviated as DMDMS),
dimethyldiethoxysilane, dimethyldiacetyloxysilane,
di-n-butyldimethoxysilane, diphenyldimethoxysilane,
trimethylmethoxysilane, tri-n-butylethoxysilane,
3-mercaptopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane,
3-methacryloyloxypropyltrimethoxysilane, or
3-methacryloyloxypropyltriethoxysilane.
[0060] Preferably, the silane monomer component also comprises a
polysiloxane represented by Formula (4-2).
##STR00007##
[0061] In Formula (4-2), each R.sub.e, R.sub.f, R.sub.g and R.sub.h
are the same or different, and each independently represents a
hydrogen atom, a C.sub.1-C.sub.10 alkyl group, a C.sub.2-C.sub.6
alkenyl group, or a C.sub.6-C.sub.15 aryl group. It is noted that
any one of the above alkyl group, alkenyl group and aryl group can
optionally have a substituent. When s is an integer from 2 to 1000,
each R.sub.e is the same or different, and R.sub.f is the same or
different. The alkyl group, for example, is methyl, ethyl or
n-propyl; the alkenyl group, for example, is vinyl, acryloyl-propyl
or methyl-acryloyloxy-propyl; the aryl group, for example, is
phenyl, tolyl, or naphthyl.
[0062] R.sub.f, and R.sub.g independently represent a hydrogen
atom, a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 acyl group,
or a C.sub.6-C.sub.15 aryl group. It is noted that any one of the
above alkyl group, acyl group and aryl group can optionally have a
substituent. The alkyl group, for example, is methyl, ethyl,
n-propyl, isopropyl, or n-butyl.; the acyl group, for example, is
acetyl; the aryl group, for example, is phenyl.
[0063] In Formula (4-2), s is an integer selected from 1 to 1000;
preferably s is an integer selected from 3 to 300; more preferably
s is an integer selected from 5 to 200.
[0064] The polysiloxane represented by Formula (4-2) can be used
singly or in combination. The polysiloxane represented by Formula
(4-2) includes but is not limited to
1,1,3,3-tetramethyl-1,3-dimethoxy disiloxane,
1,1,3,3-tetramethyl-1,3-diethoxy disiloxane,
1,1,3,3-tetraethyl-1,3-diethoxy disiloxane or the commercially
available products of silanol terminated polydimethylsiloxane
manufactured by Gelest Company (trade names such as DM-S12
(molecular weight of 400 to 700), DMS-S15 (molecular weight of 1500
to 2000), DMS-S21 (molecular weight 4200), DMS-S27 (molecular
weight 18000), DMS-S31 (molecular weight 26000), DMS-S32 (molecular
weight 36000), DMS-S33 (molecular weight 43500), DMS-S35 (molecular
weight 49000), DMS-S38 (MW 58000) DMS-S42 (molecular weight 77000)
or PDS-9931 (MW 1000-1400)).
[0065] Preferably, the silane monomer component also includes
silicon dioxide particles. The average particle diameter of the
silicon dioxide particles is not particularly limited and ranges
from 2 nm to 250 nm, preferably from 5 nm to 200 nm, and more
preferably from 10 nm to 100 nm
[0066] The silicon dioxide particles can be used singly or in
combination, and the silicon dioxide particles include but are not
limited to commercially available products manufactured by Jgc
Catalysts & Chemicals Co., Ltd. [trade names: Oscar 1132
(particle diameter of 12 nm; dispersing agent is methanol), OSCAR
1332 (particle diameter of 12 nm; dispersant n-propanol), OSCAR 105
(particle size 60 nm; dispersant y-butyrolactone), OSCAR 106
(particle diameter of 120 nm; dispersant diacetone alcohol), etc.];
commercially available products by Fuso Chemical Co. [ trade names:
Quartron PL-1-IPA (particle diameter of 13 nm; dispersant isobutyl
ketone), Quartron PL-1-TOL (particle diameter of 13 nm; dispersant
toluene), Quartron PL-2L-PGME (18 nm particle size; diacetone
alcohol propylene glycol monomethyl ether) or Quartron PL-2L-MEK
(particle size 18 nm; dispersant methyl ethyl ketone)]; or
commercially available products manufactured by Nissan Chemical
Company [trade names, such as IPA-ST (particle diameter 12 nm;
dispersant isopropanol), EG-ST (particle diameter of 12 nm;
dispersant ethylene glycol), IPA-ST-L (particle size 45 nm;
dispersant isopropanol) or IPA-ST-ZL (particle diameter of 100 nm;
dispersant isopropyl alcohol)].
[0067] A general method can be applied in the condensation
reaction, for example, adding solvents, water and optionally
catalyst in the silane monomer component, and heating and stirring
under 50.degree. C. to 150.degree. C. for 0.5 to 120 hours, and
removing byproducts (alcohols, water, etc.) by distillation with
stirring.
[0068] The solvent used in the aforementioned reaction is not
particularly limited, and the solvent can be the same or different
from the solvent (D) included in the photosensitive polysiloxane
composition according to the present invention. Based on 100 parts
by weight of the total used amount of the silane monomer component,
the used amount of the solvent is from 15 to 1200 g; preferably
from 20 to 1100 g; and more preferably from 30 to 1000 g.
[0069] Based on 1 mole of hydrolyzable groups contained in the
silane monomer component, the used amount of the water in the
aforementioned reaction is from 0.5 moles to 2 moles.
[0070] The catalyst is not particularly limited, and is preferably
selected from the group consisting of an acidic catalyst and a
basic catalyst. The acidic catalyst includes but is not limited to
hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid,
oxalic acid, phosphoric acid, acetic acid, trifluoroacetic acid,
formic acid, polybasic carboxylic acid or an anhydride thereof, or
ion exchange resins. The basic catalyst includes but is not limited
to diethylamine, triethylamine, tripropylamine, tributylamine,
tripentylamine, trihexylamine, triheptylamine, trioctylamine,
diethanolamine, triethanolamine, sodium hydroxide, and potassium
hydroxide, the amine group-containing silane having an alkoxy group
or ion exchange resins and the like.
[0071] Based on 100 parts by weight of the total used amount of the
silane monomer component, the used amount of the catalyst in the
aforementioned reaction preferably is from 0.005 g parts by weight
to 15 g parts by weight; more preferably 0.01 g parts by weight to
12 g parts by weight; and most preferably from 0.05 g parts by
weight to 10 g parts by weight.
[0072] Concerning stability, the polysiloxane (A) manufactured by
the condensation reaction preferably excludes the byproducts (such
as alcohols or water) and the catalyst. Therefore the polysiloxane
(A) can be optionally purified. The purification method is not
particularly limited. Preferably, a hydrophobic solvent is used for
the dilution of the polysiloxane (A). Subsequently, the organic
layer is washed with water several times and concentrated by a
rotary evaporator to remove the alcohols or water. In addition, ion
exchange resins can be used to remove the catalyst.
[0073] In the present invention, if the alkyl group containing the
acid anhydride group, the alkyl group containing the epoxy group or
the alkoxy group containing the epoxy group is absent in the
polysiloxane (A), the chemical resistance is poor. Though not
willing to be limited by theory, it is believed that because the
acid anhydride group and the epoxy group have excellent reactivity,
they can form a bridge between macromolecules and form a net which
has good density and chemical resistance.
[0074] The kind of the o-naphthoquinone diazide sulfonic acid ester
(B) according to the present invention is not particularly limited,
and common o-naphthoquinone diazide sulfonic acid esters can be
used. The o-naphthoquinone diazide sulfonic acid ester (B) can be
completely esterified or partially esterified ester-based
compound.
[0075] The O-naphthoquinone diazide sulfonic acid ester (B) is
preferably prepared by reacting an o-naphthoquinone diazide
sulfonic acid or salts thereof with a hydroxy compound. The
O-naphthoquinone diazide sulfonic acid ester (B) is more preferably
prepared by reacting the o-naphthoquinone diazide sulfonic acid or
salts thereof with a polyhydroxy compound.
[0076] The O-naphthoquinone diazide sulfonic acid is, for example,
o-naphthoquinone diazide-4-sulfonic acid, o-naphthoquinone
diazide-5-sulfonic acid or o-naphthoquinone diazide-6-sulfonic
acid. In addition, the o-naphthoquinone diazide sulfonic acid salts
are, for example, o-naphthoquinone diazonaphthoquinone sulfonyl
halides.
[0077] The hydroxy compound is, for example:
[0078] (1) Hydroxybenzophenone-based compounds, such as,
2,3,4-trihydroxy-benzophenone, 2,4,4'-trihydroxy-benzophenone,
2,4,6-trihydroxy-benzophenone, 2,3,4,4'-tetrahydroxy benzophenone,
2,4,2',4'-tetrahydroxy benzophenone,
2,4,6,3',4'-pentahydroxy-benzophenone,
2,3,4,2',4'-pentahydroxy-benzophenone,
2,3,4,2',5'-pentahydroxy-benzophenone,
2,4,5,3',5'-pentahydroxy-benzophenone or
2,3,4,3',4',5'-hexahydroxy-benzophenone.
[0079] (2) Hydroxyaryl-based compounds, for example, a hydroxy aryl
compound represented by Formula (5-1):
##STR00008##
[0080] in Formula (5-1), wherein, each R.sup.11 and R.sup.12
independently represents a hydrogen atom, a halogen atom or a
C.sub.1-C.sub.6 alkyl group; each R.sup.13, R.sup.14, R.sup.17
independently represents a hydrogen atom or a C.sub.1-C.sub.6 alkyl
group; each R.sup.15, R.sup.16, R.sup.18, R.sup.19, R.sup.20 and
R.sup.21 independently represents a hydrogen atom, a halogen atom,
a C.sub.1-C.sub.6 alkyl group, a C.sub.1-C.sub.6 alkoxy group, a
C.sub.1-C.sub.6 alkenyl group or a C.sub.1-C.sub.6 cycloalkyl
group; each d, e and f independently represents an integer selected
from 1 to 3; z represents 0 or 1.
[0081] The hydroxyaryl-based compounds represented in Formula (5-1)
are, for example, tris(4-hydroxyphenyl)methane,
bis(4-hydroxy-3,5-dimethyl-phenyl)-4-hydroxyphenyl methane,
bis(4-hydroxy-3,5-dimethyl-phenyl)-3-hydroxyphenyl methane,
bis(4-hydroxy-3,5-dimethyl-phenyl)-2-hydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenyl methane,
bis(4-hydroxy -2,5-dimethylphenyl)-3-hydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenyl methane,
bis(4-hydroxy-3,5-dimethylphenyl)-3,4-bis(hydroxyphenyl)methane,
bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenyl methane,
bis(4-hydroxy-3,5-dimethylphenyl)-2,4-hydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenyl methane,
bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenyl methane,
bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenyl methane,
bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenyl methane,
bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenyl methane,
bis(3-cyclohexyl-4-hydroxy-6-methyl-phenyl)-2-hydroxyphenyl
methane,
bis(3-cyclohexyl-4-hydroxy-6-methyl-phenyl)-3-hydroxyphenyl
methane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-hydroxyphenyl
methane,
bis(3-cyclohexyl-4-hydroxy-6-methyl-phenyl)-3,4-dihydroxyphenyl
methane, bis(3-cyclohexyl-6-hydroxyphenyl)-3-hydroxyphenyl methane,
bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenyl methane,
bis(3-cyclohexyl-6-hydroxyphenyl)-2-hydroxyphenyl methane,
bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-2-hydroxyphenyl methane,
bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenyl methane,
bis(3-cyclohexyl-6-hydroxy-4-methyl-phenyl)-3,4-dihydroxyphenyl
methane,
1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)
ethyl]benzene or
1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyph-
enyl)ethyl]benzene.
[0082] (3) (Hydroxyphenyl) hydrocarbon compounds, for example,
(hydroxyphenyl) hydrocarbon compounds represented by Formula
(5-2):
##STR00009##
[0083] wherein in Formula (5-2), each R.sup.22 and R.sup.23
independently represents a hydrogen atom or a C.sub.1-C.sub.6 alkyl
group; each g and h independently represents an integer selected
from 1 to 3.
[0084] The (hydroxyphenyl)-hydrocarbon compounds represented in
Formula (5-2) are, such as,
2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane,
2(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane,
2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane,
bis(2,3,4-trihydroxyphenyl)methane or
bis(2,4-dihydroxyphenyl)methane and the like.
[0085] (4) Other aromatic hydroxyl compounds are, such as phenol,
p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A,
naphthol, catechol, 1,2,3-pyrogallol methyl ether,
1,2,3-pyrogallol-1,3-dimethyl ether, 3,4,5-trihydroxy benzoic acid,
or partially esterified or etherified 3,4,5-trihydroxy benzoic
acid.
[0086] The hydroxy compound is preferably
1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene-
, 2,3,4-trihydroxy-benzophenone, 2,3,4,4'-tetrahydroxy
benzophenone, or a combination thereof. The hydroxy compounds can
be used singly or in combination.
[0087] The reaction of the o-naphthoquinone diazide sulfonic acid
or salts thereof with the hydroxy compound is usually performed in
an organic solvent, such as dioxane, N-pyrrolidone, acetamides and
etc. Furthermore, the reaction is preferably performed in an
alkaline condensing agent, such as triethanolamine, alkali metal
carbonates or alkali metal bicarbonates.
[0088] The degree of esterification of the o-naphthoquinone diazide
sulfonic acid ester (B) is preferably more than 50%. That is, based
on 100 mol % of the used amount of the hydroxyl groups in the
hydroxy compound, 50 mole % or more hydroxyl groups in the hydroxy
compound react with the o-naphthoquinone diazide sulfonic acid or
salts thereof in the esterification reaction. The degree of
esterification of the o-naphthoquinone diazide sulfonic acid ester
(B) is more preferably 60% or more.
[0089] Based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the o-naphthoquinone diazide
sulfonic acid ester (B) is from 1 part by weight to 30 parts by
weight; preferably 3 parts by weight to 25 parts by weight; and
more preferably 5 parts by weight to 20 parts by weight.
[0090] The thermal base generator (C) according to the present
invention comprises a compound represented by Formula (1) or an
salt derivative thereof and/or a compound represented by Formula
(2) and/or a compound represented by Formula (3):
##STR00010##
[0091] wherein:
[0092] m represents an integer selected from 2 to 6; and
[0093] R.sup.1 and R.sup.2 independently represent a hydrogen atom,
a C.sub.1-C.sub.8 alkyl group, a substituted or unsubstituted
C.sub.1-C.sub.6 hydroxyalkyl group, or a C.sub.2-C.sub.12
dialkylamino group;
[0094] preferably, m represents an integer selected from 3 to
5.
[0095] In one embodiment of the invention, R.sup.1 and R.sup.2
independently represent a hydrogen atom; a C.sub.1-C.sub.8 alkyl
group, for example: methyl, ethyl, isopropyl, n-butyl, tert-butyl
or n-hexyl; a substituted or unsubstituted C.sub.1-C.sub.6
hydroxyalkyl group, for example: hydroxymethyl, 2-hydroxyethyl,
2-hydroxypropyl, 2-hydroxy isopropyl, 3-hydroxy-tert-butyl or
6-hydroxyhexyl; a C.sub.2-C.sub.12 dialkylamino group, for example:
dimethylamino, methylethylamino, diethylamino, di-isopropylamino,
tert-butyl-methylamino or di-n-hexylamino.
[0096] The preferred examples of the aforementioned compound
represented by Formula (1) or the salt derivative thereof are
1,5-diazabicyclo[4.3.0]non-5-ene (DBN),
1,5-diazabicyclo[4.4.0]dec-5-ene,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
5-hydroxypropyl-1,8-diazabicyclo[5.4.0]undec-7-ene,
5-dibutylamino-1,8-diazabicyclo[5.4.0]undec-7-ene or the
commercially available products manufactured by Aporo Co., Ltd.:
U-CAT.RTM. SA810, U-CAT.RTM. SA831, U-CAT.RTM. SA841, U-CAT.RTM.
SA851, U-CAT.RTM. 5002; more preferably, DBN, U-CAT.RTM. SA851 or
U-CAT.RTM. 5002.
##STR00011##
[0097] wherein:
[0098] R.sup.3, R.sup.4, R.sup.5 and R.sup.6 independently
represent a hydrogen atom, a substituted or unsubstituted
C.sub.1-C.sub.8 alkyl group, a substituted or unsubstituted
C.sub.3-C.sub.8 cycloalkyl group, a substituted or unsubstituted
C.sub.1-C.sub.8 alkoxy group, a substituted or unsubstituted
C.sub.2-C.sub.8 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.8 alkynyl group, a substituted or unsubstituted aryl
group, or a substituted or unsubstituted heterocyclic group;
[0099] R.sup.7 and R.sup.8 independently represent a hydrogen atom,
a substituted or unsubstituted C.sub.1-C.sub.8 alkyl group, a
substituted or unsubstituted C.sub.3-C.sub.8 cylcoalkyl group, a
substituted or unsubstituted C.sub.1-C.sub.8 alkoxy group, a
substituted or unsubstituted C.sub.2-C.sub.8 alkenyl group, a
substituted or unsubstituted C.sub.2-C.sub.8 alkynyl group, a
substituted or unsubstituted aryl group, or a substituted or
unsubstituted heterocyclic group, or R.sup.7 and R.sup.8 together
form a substituted or unsubstituted monocyclic group, or R.sup.7
and R.sup.8 together form a substituted or unsubstituted polycyclic
group;
[0100] R.sup.9 represents a substituted or unsubstituted C.sub.1-C
.sub.12 alkyl group, a substituted or unsubstituted
C.sub.3-C.sub.12 cycloalkyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkenyl group, a substituted or unsubstituted
C.sub.2-C.sub.12 alkynyl group, an unsubstituted aryl group, an
aryl group substituted with a C.sub.1-C.sub.3 alkyl group, an
unsubstituted aralkyl, an aralkyl group substituted with a
C.sub.1-C.sub.3 alkyl group or a substituted or unsubstituted
heterocyclic group; the total carbon atom amount of R.sup.9 is
below 12.
##STR00012##
[0101] wherein:
[0102] R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are
as defined in Formula (2);
[0103] R.sup.10 represents a substituted or unsubstituted
C.sub.1-C.sub.12 alkylene group, a substituted or unsubstituted
C.sub.3-C.sub.12 cycloalkylene group, a substituted or
unsubstituted C.sub.2-C.sub.12 alkenylene group, a substituted or
unsubstituted C.sub.2-C.sub.12 alkynylene group, an unsbustituted
arylene group, an arylene group substituted with a C.sub.1-C.sub.3
alkyl group, an unsubstituted aralkylene group, an aralkylene group
substituted with a C.sub.1-C.sub.3 alkyl group or a substituted or
unsubstituted heterocyclic group; the total carbon atom amount of
R.sup.10 is below 12.
[0104] The preferred examples of the aforementioned compounds
represented by Formula (2) and Formula (3) are
N-(isopropoxycarbonyl)-2,6-dimethyl piperidine,
N-(isopropoxycarbonyl)-2,2,6,6-tetramethyl piperidine,
N-(isopropoxycarbonyl)diisopropylamine, N-(isopropoxycarbonyl)
pyrrolidine, N-(isopropoxycarbonyl)-2,5-dimethyl pyrrolidine,
N-(isopropoxycarbonyl)azetidine,
N-(1-ethylpropoxycarbonyl)-2,6-dimethyl piperidine,
N-(1-ethylpropoxycarbonyl)-2,2,6,6-tetramethyl piperidine,
N-(1-ethylpropoxycarbonyl)diisopropylamine,
N-(1-ethylpropoxycarbonyl)pyrrolidine,
N-(1-ethylpropoxycarbonyl)-2,5-dimethyl pyrrolidine,
N-(1-ethylpropoxycarbonyl)azetidine,
N-(1-propylbutoxycarbonyl)-2,6-dimethyl piperidine,
N-(1-propylbuloxycarbonyl)-2,2,6.6-tetramethyl piperidine,
N-(1-propylbutoxcarbonisopropylamine,
N-(1-propylbutoxarbonyl)pyrrolidine,
N-(1-propylbutoxycarbonyl)-2,5-dimethyl pyrrolidine,
N-(1-propylbutoxycarbonyl)azetidine,
N-(cyclopenlyloxycarbonyl)-6-dimethyl piperidine,
N-(cyclopentyloxycarbonyl)-2,2,6,6-tetramethyl piperidine,
N-(cyclopentloxycarbonyl)diisopropylamine,
N-(cyclopentyloxycarbonyl)pyrrolidine,
N-(cyclopentyloxycarbonyl)-2,5-dimethyl pyrrolidine,
N-(cyclopentyloxycarbonyl)azetidine,
N-(cyclohexylcarbonyl)-2,6-dimethyl piperidine,
N-(cyclohexylcarbonyl)-2,2,6,6-tetramethyl piperidine,
N-(cyclohexylcarbonyl)diisopropylamine,
N-(cyclohexylcarhonyl)pyrrolidine,
(cyclohexylcarbonyl)-2,5-dimethyl pyrrolidine,
N-(cyclohexylcarbonyl)azetidine,
N-(tert-butoxycarbonyl)-2,6-dimethyl piperidine,
N-(tert-buloxycarbonyl)-2,2,6,6-tetramethyl piperidine,
N-(tert-butoxycarbonyl)diisopropylamine,
N-(tert-butoxycarbonyl)pyrrolidine,
N-(tert-butoxycarbonyl)-2,5-dimethyl pyrrolidine,
N-(tert-butoxycarbonyl)azetidine,
N-(benzyloxycarbonyl)-2,6-dimethyl piperidine,
N-(benzyloxycarbonyl)-2,2,6,6-tetramethyl piperidine,
N-(benzyloxycarbonyl)diisopropylamine,
N-(benzyloxycarbonyl)pyrrolidine,
N-(benzyloxycarbonyl)-2,5-dimethyl pyrrolidine,
N-(benzyloxycarbonyl)azetidin or
1,4-bis(N,N'-diisopropylaminocarbonyl)cyclohexane; preferably
N-(isopropoxycarbonyl)-2,6-dimethyl piperidine,
N-(1-ethylpropoxycarbonyl)diisopropylamine,
(cyclopentyloxycarbonyl)-2,6-dimethyl piperidine,
N-(benzyloxycarbonyl)pyrrolidine or
1,4-bis(N,N'-diisopropylaminocarbonyl)cyclohexane.
[0105] Based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the thermal base generator (C)
is from 0.05 parts by weight to 20 parts by weight; preferably from
0.1 parts by weight to 18 parts by weight; and more preferably from
0.1 parts by weight to 15 parts by weight.
[0106] If the thermal base generator (C) is absent, the resulted
thin film formed has poor chemical resistance. Though not willing
to be limited by theory, it is believed that because the thermal
base generator (C) can produce a base substance by heating, and it
can enhance the cross-linked reaction of the polysiloxane (A) in
post-baking by forming a dense net to improve the chemical
resistance.
[0107] The kind of the solvent (D) according to the present
invention is not particularly limited. The solvent (D) is, for
example, a compound containing an alcoholic hydroxy group or a
cyclic compound containing a carbonyl group.
[0108] The compound containing the alcoholic hydroxy group is, for
example, acetol, 3-hydroxy-3-methyl-2-butanone,
4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone,
4-hydroxy-4-methyl-2-pentanone (also called as diacetone alcohol,
DAA), ethyl lactate, butyl lactate, propylene glycol monomethyl
ether, propylene glycol monoethyl ether (PGEE), propylene glycol
monomethyl ether acetate (PGMEA), propylene glycol mono-n-propyl
ether, propylene glycol mono-n-butyl ether, propylene glycol
mono-t-butyl ether, 3-methoxy-1-butanol,
3-methyl-3-methoxy-1-butanol or a combination thereof. It is noted
that the compound containing the alcoholic hydroxy group is
preferably diacetone alcohol, ethyl lactate, propylene glycol
monoethyl ether, propylene glycol methyl ether acetate or
combinations thereof. The compound containing the alcoholic hydroxy
group can be used singly or in combination.
[0109] The cyclic compound containing the carbonyl group is, for
example, .gamma.-butyrolactone, .gamma.-valerolactone,
.delta.-valerolactone, propylene carbonate, N-methyl pyrrolidone,
cyclohexanone or cycloheptanone. It is noted that the cyclic
compound containing the carbonyl group is preferably
.gamma.-butyrolactone, N-methyl pyrrolidone, cyclohexanone or
combinations thereof. The cyclic compound containing the carbonyl
group may be used singly or in combination.
[0110] The compound containing the alcoholic hydroxy group can be
used in combination with the cyclic compound containing the
carbonyl group, and the mixing weight ratio of both is not
particularly limited. The weight ratio of the compound containing
the alcoholic hydroxy group and the cyclic compound containing the
carbonyl group ranges preferably from 99/1 to 50/50; more
preferably from 95/5 to 60/40. It is noted that when the weight
ratio of the compound containing the alcoholic hydroxy group and
the cyclic compound containing the carbonyl group is from 99/1 to
50/50 in the solvent (D), the unreacted silanol (Si--OH) groups in
the polysiloxane (A) are unlikely to carry on a condensation
reaction and storage stability is lowered. In addition, since the
compound containing the alcoholic hydroxy group and the cyclic
compound containing the carbonyl group have good compatibility with
the o-naphthoquinone diazide sulfonic acid ester (B), a whitening
phenomenon hardly occurs in the coating film and the transparency
of the thin film can be maintained.
[0111] Without lowering the effect of the present invention, other
solvents can be included. These other solvents can be, for example:
(1) esters: ethyl acetate, n-propyl acetate, iso-propyl acetate,
n-butyl acetate, isobutyl acetate, propylene glycol monomethyl
ether acetate, 3-methoxy-1-butyl acetate or
3-methyl-3-methoxy-1-butyl acetate, etc.; (2) ketones: methyl
isobutyl ketone, diisopropyl ketone, or di-isobutyl ketone, etc.;
or (3) ethers: diethyl ether, diisopropyl ether, di-n-butyl ether
or diphenyl ether etc.
[0112] Based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the solvent (D) is from 100
parts by weight to 1200 parts by weight; preferably from 150 parts
by weight to 1000 parts by weight; and more preferably from 200
parts by weight to 800 parts by weight.
[0113] The photosensitive polysiloxane composition of the present
invention can optionally further include an additive (E). The
additive (E) can be, for example, a sensitizer, adhesion auxiliary
agent, surfactant, dissolution promoter, defoamer, or combinations
thereof.
[0114] The kind of the sensitizer is not particularly limited. The
sensitizer can use preferably a compound containing a phenolic
hydroxyl group, for example:
[0115] (1) a trisphenol type compound: such as
tris(4-hydroxyphenyl)methane,
bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenyl methane,
bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenyl methane,
bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenyl methane,
bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenyl methane,
bis(4-hydroxy-3,5-methylphenyl)-2-hydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenyl methane,
bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenyl methane,
bis(4-hydroxy-2,5-dimethylphenyl)-2,4-bis(hydroxyphenyl)methane,
bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenyl methane,
bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenyl methane,
bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenyl methane,
bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenyl methane
or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenyl
methane, etc.;
[0116] (2) a bisphenol type compound: such as
bis(2,3,4-trihydroxyphenyl)methane,
bis(2,4-dihydroxyphenyl)methane,
2,3,4-trihydroxyphenyl-4'-hydroxyphenyl methane,
2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl) propane,
2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane,
2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane,
2-(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane,
2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane,
2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane or
2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane
and the like;
[0117] (3) a polynuclear branched compounds: such as
1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl
or 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis
(3-methyl-4-hydroxyphenyl)ethyl]benzene and the like;
[0118] (4) a condensation type phenol compound: such as
1,1-bis(4-hydroxyphenyl)cyclohexane, etc.;
[0119] (5) a polyhydroxy benzophenones: such as 2,3,4-trihydroxy
benzophenone, 2,4,4'-trihydroxy benzophenone, 2,4,6-trihydroxy
benzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone,
2,3,4,4'-tetrahydroxy benzophenone, 2,4,2',4'-tetrahydroxy
benzophenone, 2,4,6,3',4'-pentahydroxy benzophenone,
2,3,4,2',4'-pentahydroxy benzophenone, 2,3,4,2',5'-pentahydroxy
benzophenone, 2,4,6,3',4',5'-hexahydroxy benzophenone or
2,3,4,3',4',5'-hexahydroxy benzophenone; or
[0120] (6) combinations of the aforementioned compounds containing
the phenolic hydroxyl group.
[0121] Based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the sensitizer is from 5 parts
by weight to 50 parts by weight; preferably from 8 parts by weight
to 40 parts by weight; and more preferably from 10 parts by weight
to 35 parts by weight.
[0122] The adhesion auxiliary agent is, for example, a melamine
compound, and a silane-based compound. The role of the adhesion
auxiliary agent is to increase the adhesion between the device or
component and the thin film that is formed by the photosensitive
polysiloxane composition.
[0123] Commercially available products of melamine compounds are,
for example, manufactured by Mitsui Chemicals, trade names Cymel
300, Cymel-303, etc.; or the products manufactured by Sanwa
Chemical, trade names MW-30MH, MW-30, MS-11, MS-001, MX-750 or
MX-706.
[0124] When using the melamine compound as the adhesion auxiliary
agent, based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the melamine compound is from
0 part by weight to 20 parts by weight; preferably from 0.5 parts
by weight to 18 parts by weight; and more preferably from 1.0 part
by weight to 15 parts by weight.
[0125] The silane-based compound is, for example,
vinyltrimethoxysilane, vinyltriethoxysilane,
3-acryloxypropyltrimethoxysilane, vinyl
tris(2-methoxyethoxy)silane,
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyldimethylmethoxysilane,
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
3-chloropropylmethyldimethoxysilane,
3-chloropropyltrimethoxysilane,
3-methacryloxypropyltrimethoxysilane,
3-mercaptopropyltrimethoxysilane or a commercially available
product manufactured by Shin-Etsu Chemical Company (trade name of
KBM403).
[0126] When using the silane-based compound as the adhesion
auxiliary agent, based on 100 parts by weight of the used amount of
the polysiloxane (A), the used amount of the silane-based compound
is 0 part by weight to 2 parts by weight; preferably 0.05 parts by
weight to 1 part by weight; and more preferably 0.1 parts by weight
to 0.8 parts by weight.
[0127] The surfactants are, for example, anionic surfactants,
cationic surfactants, nonionic surfactants, amphoteric surfactants,
polysiloxane-based surfactants, fluorine-based surfactants or a
combination thereof.
[0128] Examples of the surfactant include (1) polyoxyethylene alkyl
ethers: polyoxyethylene lauryl ether, etc.; (2) polyoxyethylene
phenyl ethers: polyoxyethylene octyl phenyl ether, polyoxyethylene
nonyl phenyl ether, etc.; (3) polyethylene glycol diesters:
polyethylene glycol dilaurate, polyethylene glycol distearate,
etc.; (4) sorbitan fatty acid esters; and (5) fatty acid modified
poly esters; and (6) tertiary amine modified polyurethanes.
Commercially available products of surfactant are, for example, KP
(manufactured by Shin-Etsu Chemical), SF-8427 (manufactured by Dow
Corning Toray Silicone Co., Ltd.), Polyflow (manufactured by
Kyoeisha Grease Chemical), F-Top (manufactured by Tochem Products
Co., Ltd.), Megaface (manufactured by Dainippon ink chemical
industry (DIC)), Fluorade (by Sumitomo 3M Co., Ltd.), Surflon
(manufactured by Asahi Glass), SINOPOL E8008 (Sino Japan Chemical
Co. Ltd.), F-475 (manufactured by Dainippon ink chemical industry)
or combinations thereof.
[0129] Based on 100 parts by weight of the used amount of the
polysiloxane (A), the used amount of the surfactant is from 0.5
parts by weight to 50 parts by weight; preferably from 1 part by
weight to 40 parts by weight; and more preferably from 3 parts by
weight to 30 parts by weight.
[0130] Examples of the defoamer include Surfynol MD-20, Surfynol
MD-30, EnviroGem AD01, EnviroGem AE01, EnviroGem AE02, Surfynol
DF110D, Surfynol 104E, Surfynol 420, Surfynol DF37, Surfynol DF58,
Surfynol DF66, Surfynol DF70 and Surfynol DF210 (manufactured by
Air products) and the like. Based on 100 parts by weight of the
used amount of the polysiloxane (A), the used amount of the
defoamer is from 1 part by weight to 10 parts by weight; preferably
from 2 parts by weight to 9 parts by weight; and more preferably
from 3 parts by weight to 8 parts by weight.
[0131] Examples of the dissolution promoter include
N-hydroxydicarboxylic imide and a compound containing a phenolic
hydroxyl group. For example, the dissolution promoter is the
compound containing the phenolic hydroxyl group used in the
o-naphthoquinone diazide sulfonic acid ester (B). Based on 100
parts by weight of the used amount of the polysiloxane (A), the
used amount of the dissolution promoter is from 1 part by weight to
20 parts by weight; preferably from 2 parts by weight to 15 parts
by weight; and more preferably from 3 parts by weight to 10 parts
by weight.
[0132] The photosensitive polysiloxane composition can be prepared
in the following manner: placing the polysiloxane (A), the
o-naphthoquinone diazide sulfonic acid ester (B), the thermal base
generator (C) and the solvent (D) in a blender and stirring them
until homogeneously mixed into a solution state. If necessary, the
additive (E) can be added.
[0133] The present invention also provides a method for forming a
thin film on a substrate comprising applying the photosensitive
polysiloxane composition as mentioned above on the substrate.
[0134] The present invention also provides a thin film on a
substrate, which is manufactured by the method as mentioned
above.
[0135] The present invention further provides a device comprising
the thin film. Preferably, the thin film is a planarization film of
a TFT substrate in a liquid crystal display element or organic
light-emitting display device, an interlayer insulating film or an
overcoat of a core material or a protective material in a
waveguide.
[0136] The following descriptions detail the method of forming the
thin film, comprising: using a photosensitive polysiloxane
composition to form a pre-baked coating film, pattern-exposing of
the pre-baked coating film, removing the unexposed region of the
film by an alkali developer to form a pattern, and performing a
post-baking treatment to form the thin film.
[0137] Forming a Pre-Baked Coating Film
[0138] By spin coating, cast coating, or roll coater coating
method, the photosensitive polysiloxane composition in the above
solution state is coated onto the device to be protected
(hereinafter referred to as substrate), to form a coating film.
[0139] The above-mentioned substrate can be alkali-free glass, soda
lime glass, Pyrex glass, quartz glass, or glasses adhered with a
transparent conductive film used in a liquid crystal display
device, or a substrate (such as, silicon substrate) used in the
photoelectric conversion device (such as a solid-state imaging
device).
[0140] After forming the coating film, most of the organic solvent
of the photosensitive polysiloxane composition is removed by
reducing pressure and drying method, and then all the residual
organic solvent is removed completely by pre-baking method, to form
a pre-baked coating film.
[0141] The above-mentioned operation condition can be different
according to the kinds of the components and ratio. Generally,
reducing pressure and drying are at a pressure of 0 to 200 Torr for
1 second to 60 seconds, and pre-baking is at a temperature between
70.degree. C. to 110.degree. C. for 1 minute to 15 minutes.
[0142] Pattern-Exposing
[0143] A mask having a specific pattern is used to perform exposure
for the above-mentioned pre-baked coating film. The light used in
the exposure process, is preferably ultraviolet (UV) rays (g line,
b line, i line, etc.), and the device used to provide UV rays can
be an ultra high-pressure mercury lamp or a metal halide lamp.
[0144] Developing
[0145] Unnecessary portions of the above exposed pre-baked coating
film are removed by immersing the pre-baked coating film in the
developer solution at a temperature between 23.+-.2.degree. C. and
developing for about 15 seconds to 5 minutes, so as to form a
semi-finished product of the thin film with a predetermined pattern
on the substrate. The developer can be alkaline compounds, such as,
sodium hydroxide, potassium hydroxide, sodium carbonate, sodium
hydrogen carbonate, potassium carbonate, potassium bicarbonate,
sodium silicate, sodium methylsilicate, aqueous ammonia,
ethylamine, diethylamine, dimethyl ethanolamine,
tetramethylammonium hydroxide (THAM), tetraethylammonium hydroxide,
choline, pyrrole, piperidine, or
1,8-diaza-bicyclo-(5,4,0)-7-undecene.
[0146] It is noted that if the concentration of the developer is
too high, the specific pattern may be damaged or the resolution of
the specific pattern may be deteriorated. If the concentration of
the developer is too low, poor development may happen, and the
specific pattern may not be formed or residues of the composition
remain in the exposed portions. Therefore, the concentration of the
developer affects the formation of the subsequent specific pattern
of the photosensitive polysiloxane composition after exposure. The
concentration range of the liquid developer is preferably from
0.001 wt % to 10 wt %; more preferably from 0.005 wt % to 5 wt %;
further more preferably from 0.01 wt % to 1 wt %. The present
embodiment of the present invention employs a developer of 2.38 wt
% tetramethylammonium hydroxide. It is noted that even using a
lower concentration of the developer, the photosensitive
polysiloxane composition of the present invention is capable of
forming a fine pattern.
[0147] Post-Baking
[0148] The substrate (semi-finished product of the thin film with
the predetermined pattern on the substrate) is washed with water to
remove the unwanted portions of the above-mentioned exposed
pre-baked coating film. Then, compressed air or compressed nitrogen
is used to dry up the semi-finished product of the thin film with
the predetermined pattern. Finally, the semi-finished product of
the thin film with the predetermined pattern is post-baked on a
heating plate or in an oven. The heating temperature is set between
100.degree. C. to 250.degree. C., and the heating time with the
heating plate is 1 to 60 minutes or the heating time with the oven
is 5 to 90 minutes. Thereby, the semi-finished product of the thin
film with the predetermined pattern is cured to form a thin
film.
[0149] The present invention will provide more details hereinafter
in the following embodiments, but it should be understood that
these examples are only illustrative and for illustrative purposes
and should not be construed to limit the present invention.
[0150] Synthesis of Polysiloxane (A-1)
[0151] Following adding 0.30 mole of methyltrimethoxysilane
(hereinafter referred to as MTMS), 0.65 mole of
phenyltrimethoxysilane (hereinafter referred to as PTMS), 0.05 mole
of 3-(triethoxysilyl) propyl succinic anhydride (hereinafter
referred to as GF-20) and 200 g of propylene glycol monoethyl ether
(hereinafter referred to PGEE) into a 500 ml three-necked flask, an
aqueous oxalic acid solution (0.40 g oxalic acid/75 g water) was
added at room temperature with stirring within 30 minutes. Next,
the flask was immersed at 30.degree. C. in oil bath and stirred for
30 minutes. Then, within 30 minutes, the temperature of the oil
bath was raised to 120.degree. C. After the solution temperature
was dropped to 105.degree. C., heating was resumed with stirring
for polymerization for 6 hours. Then again, the solvent was removed
using distillation to obtain the polysiloxane (A-1). The kinds and
used amounts of the raw materials of the polysiloxane (A-1) are
shown in Table 1.
[0152] Synthesis of Polysiloxane (A-2) to (A-5)
[0153] Synthesis examples (A-2) to (A-5) were practiced with the
analogous method as in Synthesis example (A-1) by using various
kinds or amounts of the components of the silane monomer and
polysiloxane which are listed in Table 1. The amounts of solvent
and oxalic acid, the reaction temperature and the time of
polymerization and condensation are different from those of the
aforementioned polysiloxane (A-1) which are also listed in Table
1.
TABLE-US-00001 TABLE 1 Composition Catalyst (g) silane
monomer/polysiloxane (mol) Solvent (g) DI Oxalic Temp. Time
Preparation MTMS DMDMS PTMS PTES GF-20 TMSG TMSOX-D DMS-S27 PGEE
DAA water acid (.degree. C.) (hour) A-1 0.30 0.65 0.05 200 75 0.40
105 6 A-2 0.40 0.40 0.15 0.03 0.02 100 100 75 0.40 110 5 A-3 0.60
0.35 0.05 200 75 0.35 105 6 A-4 0.65 0.25 0.09 0.01 200 75 0.45 110
6 A-5 0.65 0.35 200 75 0.45 110 6 MW MTMS methyltrimethoxysilane
136 DMDMS dimethyldimethoxysilane 120 PTMS phenyltrimethoxysilane
198 PTES phenyltriethoxysilane 240 GF-20 3-(triethoxysilyl)propyl
succinic anhydride 304 TMSG 3-(trimethoxysilyl)propyl glutaric
anhydride 276 TMSOX-D 2-oxetanylbutoxypropyltrimethoxysilane 278
DMS-S27 the silanol end portion of polysiloxane(manufactured by
Gelest Co., Ltd.) 18000 PGEE propylene glycol monoethyl ether 104
DAA diacetone alcohol 116 DI water 18 Oxalic acid 90
EXAMPLE 1
[0154] One-hundred parts by weight of the used amount of the
polysiloxane (A-1), 1 part by weight of the ortho-naphthoquinone
diazide sulfonic acid ester (B-1) formed from
1-[1-(4-hydroxyphenyl) isopropyl]-4-[1,1-bis(4-hydroxyphenyl)
ethyl]benzene and ortho-naphthoquinone diazide-5-sulfonic acid, and
0.05 parts by weight of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)
(C-1) were mixed and dissolved in 100 parts by weight of the
propylene glycol monomethyl ether acetate (D-1) completely, so as
to form the photosensitive polysiloxane composition of Example
1.
[0155] Formation of Thin Film on Glass
[0156] Various photosensitive polysiloxane compositions were cast
coated independently on a prime glass substrate of
100.times.100.times.0.7 mm in size, and then pre-baked for 2
minutes at 100.degree. C. to obtain a pre-baked coating film of
about 2 .mu.m in thickness. And then, the pre-baked coating film
was placed under the light mask with a given pattern, and
ultraviolet light of 100 mJ/cm.sup.2 was used to irradiate the
film. Afterwards, the exposed coating film was immersed in 2.38%
TMAH solution for 60 seconds at 23.degree. C. to remove the
unexposed parts, and then the film was washed with pure water; and
placed under the light mask with the given pattern, and exposed
with the ultraviolet light of 200 mJ/cm.sup.2. Finally, the film
was post-baked for 60 minutes at 230.degree. C., so as to form the
film on the prime glass substrate.
[0157] The evaluation results of the thin film of Example 1 are
shown in Table 2.
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 to 3
[0158] Examples 2 to 8 and Comparative Examples 1 to 3 were
practiced with the same method as in Example 1 by using various
kinds or amounts of the components, the formulas. The evaluation
results of which are also listed in Table 2.
[0159] Evaluation
[0160] Chemical Resistance
[0161] Various photosensitive polysiloxane compositions were spin
coated independently on a prime glass substrate of
100.times.100.times.0.7 mm.sup.3 in size to obtain a pre-baked
coating film of about 2 .mu.m in thickness, and then pre-baked for
2 minutes at 110.degree. C. And then, the pre-baked coating film
was placed under the light mask with a given pattern, and
ultraviolet light of 100 mJ/cm.sup.2 was used to irradiate the
film. Afterwards, the exposed coating film was immersed in 2.38%
tetramethylammonium hydroxide solution for 60 seconds to remove the
exposed parts, and then the film was washed with pure water; and
placed under the light mask with the given pattern, and exposed
with the ultraviolet light of 200 mJ/cm.sup.2. And then, the film
was post-baked at different time at 230.degree. C. Afterwards, the
post-baked film was immersed in TOK106 solution for 6 minutes at
60.degree. C., and film thickness change rate is evaluated by the
following Formula:
Film Thickness Change Rate=[(thickness after immersed-thickness
before immersed)/thickness before immersed].times.100%
[0162] preferable film thickness change rate is form
-3%.about.3%.
[0163] .COPYRGT.: 3% .quadrature. film thickness change rate
.quadrature.-3%,
[0164] .smallcircle.: 5% .quadrature. film thickness change
rate>3% or -3%>film thickness change rate
.quadrature.-5%,
[0165] X: film thickness change rate>5% or film thickness change
rate<-5%.
TABLE-US-00002 TABLE 2 Comparative Example Example Composition 1 2
3 4 5 6 7 8 1 2 3 polysiloxane (A) A-1 100 100 100 (parts by
weight) A-2 100 80 30 A-3 100 50 A-4 100 50 70 A-5 20 100 100
o-naphthoquinone B-1 1 5 10 10 30 10 20 20 15 diazide sulfonic B-2
5 20 10 20 acid ester (B) (parts by weight) thermal base C-1 0.05
10 generator (C) C-2 0.1 (parts by weight) C-3 5 5 C-4 5 10 C-5 10
C-6 1 C-7 5 C-8 15 Solvent (D) D-1 100 500 300 500 1000 500 500
(parts by weight) D-2 300 500 300 500 D-3 200 500 additive (E) E-1
3 (parts by weight) E-2 0.5 Evaluation Chemical .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. X X X Resistance B-1
ortho-naphthoquinone diazide sulfonic acid ester formed from
1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]
benzene and ortho-naphthoquinone diazide-5-sulfonic acid B-2
ortho-naphthoquinone diazide sulfonic acid ester formed from
2,3,4-trihydroxy-benzophenone and ortho-naphthoquinone
diazide-5-sulfonic acid C-1 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)
C-2 U-CAT .RTM. SA851 C-3 U-CAT .RTM. 5002 C-4
N-(isopropoxycarbonyl)-2,6-dimethyl piperidine C-5
N-(1-ethylpropoxycarbonyl) diisopropylamine C-6
N-(cyclopentyloxycarbonyl)-2,6-dimethyl piperidine C-7
N-(benzyloxycarbonyl) pyrrolidine C-8 1,4-bis
(N,N'-diisopropylaminecarbonyl) cyclohexane D-1 propylene glycol
monomethyl ether acetate D-2 4-hydroxy-4-methyl-2-pentanone D-3
cyclohexanone E-1 SF-8427 (manufactured by Dow Corning Toray
Silicone Co., Ltd., surfactant) E-2 3-glycidoxypropyl trimethoxy
silane (trade name of KBM403, manufactured by Shin-Etsu Chemical
Company, adhesion auxiliary agent)
[0166] While embodiments of the present invention have been
illustrated and described, various modifications and improvements
can be made by persons skilled in the art. It is intended that the
present invention is not limited to the particular forms as
illustrated, and that all modifications not departing from the
spirit and scope of the present invention are within the scope as
defined in the following claims.
* * * * *